Non-continuous mesh structures

ABSTRACT

An article comprising a flexible mesh layer pliable enough for being arranged in direct planar contact with a contoured surface, the mesh layer providing one or more attributes of adhering, sealing or reinforcing to a surface receiving the flexible mesh.

TECHNICAL FIELD

The present invention relates generally to adhesive, sealant andstructural materials which can be formed as a mesh prior to installationin a location requiring adhering, sealing or structural support.

BACKGROUND

A variety of industries utilize polymer-based materials for sealing andadhering. The use of adhesives and sealants is widespread in theautomotive and construction industries as well as in certain consumerproduct industries such as sporting equipment, shoes, furniture andother goods where strong adhesion and sealing is necessary. However,there are often challenges in locating, using and activating suitableadhesives and sealants onto structures for a variety of reasons. Theadhesive/sealant material may be tacky and difficult to handle, it mayhave a low viscosity, it may be too rigid for application to a curvedsurface, or it may be too brittle upon cure. In addition, a curedadhesive/sealant may cause deformation to the surface to which it isapplied. Furthermore, there is an ongoing effort in many industries tolighten the weight of articles. Efforts to do so often entail reducingthe amount of material used for adhering, sealing or providingstructural support to an article. However, in reducing the amount ofsuch materials, their efficacy may also be reduced. Furthermore,manufacturing time is increased in the event that material amounts arereduced by only placing the material in select locations.

Notwithstanding the above, there remains a need for effectively reducingthe weight of a structure by modifying the format of adhesives, sealantsand structural materials. There is a further need for providing amodified sealant material so that it has a requisite amount of strengthand structure so that it can be easily die cut to a desired shape andeasily applied to a surface with reduced handling challenges. Suchmodified adhesives, sealants and structural materials may thus beapplied in a shape or foam as required and then later activated in someway (e.g., activated to foam, adhere, cure or the like). There is also aneed for formation techniques that can allow adhesives, sealants andstructural materials to be easily customized to a necessary shape, size,or structure.

SUMMARY OF THE INVENTION

One or more of the above needs are met by the present teachings which anarticle, comprising at least one solid material layer and a flexiblemesh layer pliable enough for being arranged in direct planar contactwith a contoured surface, the mesh layer providing one or moreattributes of adhering, sealing or reinforcing the solid material layer.

The teachings herein are directed to a an article, comprising a flexiblemesh layer pliable enough for being arranged in direct planar contactwith a contoured surface, the mesh layer comprising an activatablematerial and providing one or more attributes of adhering, sealing,reinforcing or acting as a handling film to a surface receiving the meshlayer.

The article may include a solid material layer which receives the meshlayer. The article may include a plurality of rigid spheres dispersed onthe solid material layer. The solid material layer may have a thickness(t) and the plurality of rigid spheres may have a max diameter (d)wherein the thickness t is greater than the max diameter d. The articlemay include a metallic component. The metallic component may comprise aplurality of metallic spheres dispersed onto the solid material layer.The metallic spheres may comprise aluminum oxide spheres. The metalliccomponent may be a metallic filler included in the activatable material.The metallic filler may allow for induction heating of the activatablematerial. The article may be located in contact with an end of a draintube to seal an interface between a drain tube and vehicle structure towhich the drain tube is attached. The flexible mesh layer may be formedas a sleeve.

The activatable material may be an expandable material. The flexiblemesh may be located onto a vehicle pillar, rocker or other vehicle framemember. The flexible mesh may be sufficiently flexible that it collapsesunder its own weight when held at one end. The flexible mesh may beformed having a plurality of repeating generally diamond shaped,rectangular, circular or square openings. A fastener may be located intoan opening of the flexible mesh to hold the mesh in place at a desiredlocation. The fastener may have a head portion having a diameter that islarger than the diameter of the opening in the flexible mesh thatreceives the fastener. The activatable material may expand upon exposureto a stimulus and any openings in the mesh become closed as a result ofexpansion of the material. The openings formed in the mesh may allow fora consistent thickness of the activatable material post expansion andmay prevent unwanted surface irregularities from forming in the expandedmaterial.

The activatable material may include a magnetic filler allowing theflexible mesh to be magnetically adhered to a metallic surface prior toactivation. The activatable material may be a sound and/or vibrationdamping material. The flexible mesh may be laminated onto a metallicshim stock layer. The flexible mesh may be included as a layer within acomposite structure. The flexible mesh may be located onto an aluminumsurface, a steel surface, a polyethylene terephthalate, or athermoplastic epoxy surface. The flexible mesh may comprise athermoplastic epoxy material. The flexible mesh may be heat bonded orotherwise adhered to a woven or non-woven fibrous material. The flexiblemesh may be located onto a panel structure for forming a patch tostiffen the panel structure.

The openings formed in the mesh may assist in reducing read-through onthe panel surface that opposes the patch. The flexible mesh may beutilized in an injection molding process to provide dimensionalstability to an injection molded material. The flexible mesh may belocated onto a first surface of an adhesive or sealant material as ahandling layer and the second surface of the adhesive or sealantmaterial is covered by a release liner. The release liner may beperforated and a plurality of metallic spheres are located onto theperforated portions of the adhesive or sealant material so that themetallic spheres adhere to the adhesive or sealant only at theperforated portions where the adhesive or sealant is exposed. Aplurality of metallic spheres may be located onto the adhesive orsealant material through the openings in the flexible mesh so that themetallic spheres adhere to the adhesive or sealant only at the openingsin the flexible mesh where the adhesive or sealant is exposed. Themetallic spheres may be located into a tray and the adhesive or sealantis brought into contact with the tray so that the metallic spheresadhere to the adhesive or sealant where it is exposed. The perforationsmay be formed in a desired pattern so that the metallic spheres arelocated in only specific locations as required for sealing a joint orfacilitating an induction heating process.

The metallic spheres may be heated prior to deposition onto the article.The flexible mesh may be formed by extrusion, die-cutting, or lasercutting. Each opening in the flexible mesh may receive an average of atleast 1 metallic sphere, at least 3 metallic spheres, at least 4metallic spheres, at least 6 metallic spheres or even at least 8metallic spheres. The flexible mesh may be located onto a vehiclesurface for bonding to an interior vehicle component. The interiorvehicle component may include one or more curved surfaces and theflexible nature of the flexible mesh allows for conforming to the shapeof the vehicle component. The flexible mesh may be formed of a materialthat expands which provides a soft interface material between thevehicle surface and the interior vehicle component. The flexible meshmay be formed of at least two distinct materials. A first material maybe laid in a first direction and a second material may be laid in asecond direction that is different from the first direction. Theflexible mesh may be located onto a fiberglass layer. The mesh may belocated onto a vehicle door beam.

The teachings herein further contemplate use of the article of any oneof the preceding claims as an acoustic blanket. The teachings are alsodirected to a method comprising extruding a sealant material layer,laminating a mesh handling material layer onto the first sealantmaterial layer to form a composite sealing structure, die-cutting thecomposite sealing structure to form a desired shape and dispensing aplurality of rigid spheres onto the composite sealing structure, so thatthe rigid spheres adhere to the sealant material but not the meshhandling layer. The method may also include locating the compositesealing structure in between two members to seal a joint between the twomembers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of one illustrative embodiment inaccordance with the present teachings.

FIG. 2 is a perspective view of a mesh applied to a solid materiallayer.

DETAILED DESCRIPTION

The present teachings meet one or more of the above needs by theimproved devices and methods described herein. The explanations andillustrations presented herein are intended to acquaint others skilledin the art with the teachings, its principles, and its practicalapplication. Those skilled in the art may adapt and apply the teachingsin its numerous forms, as may be best suited to the requirements of aparticular use. Accordingly, the specific embodiments of the presentteachings as set forth are not intended as being exhaustive or limitingof the teachings. The scope of the teachings should, therefore, bedetermined not with reference to the above description, but shouldinstead be determined with reference to the appended claims, along withthe full scope of equivalents to which such claims are entitled. Thedisclosures of all articles and references, including patentapplications and publications, are incorporated by reference for allpurposes. Other combinations are also possible as will be gleaned fromthe following claims, which are also hereby incorporated by referenceinto this written description.

This application claims the benefit of the filing date of U.S.Provisional Application No. 62/302,473, filed Mar. 2, 2016, the entiretyof the contents of that application being hereby incorporated byreference for all purposes.

The adhesive, sealing and reinforcing materials described herein arepreferably formed (e.g., molded, cut, extruded, die-cut or the like) asa non-continuous or “mesh” material including a plurality of sequentialopenings. It is possible that each opening will have the same shape andsize of any adjacent openings such that each opening is identical.However it is also possible that the openings be formed in differingshapes and sizes. The flexible mesh may be formed having a plurality ofrepeating generally diamond shaped, rectangular, circular or squareopenings. The resulting mesh may be a flexible material such that itwould collapse under its own weight when held at an end. The flexiblenature of the mesh may allow it to be located onto a curved (e.g.,contoured) surface so that it lies in direct planar contact with acurved surface. As a result adhesion/sealing is typically more uniformand avoids deformation of any surfaces opposing the surface adhered to.The flexible mesh layer may be formed as a sleeve.

The mesh may be applied as a handling layer to a solid material layer.It is also possible that as a handling layer, the openings in the meshpermit the addition of particles (e.g., spheres, metallic spheres, orthe like). Thus, the solid material may receive a plurality of rigidspheres dispersed on the solid material layer. The solid material layermay have a thickness (t) and the plurality of rigid spheres may have amax diameter (c) wherein the thickness t is greater than the maxdiameter d.

The mesh may be formed of a material having a metallic component. Themetallic component may be a metallic filler included in the activatablematerial. The metallic filler may allow for induction heating of theactivatable material.

The mesh may be located in contact with an end of a drain tube to sealan interface between a drain tube and vehicle structure to which thedrain tube is attached. The flexible mesh may be located onto a vehiclepillar, rocker or other vehicle frame member. The flexible mesh may belaminated onto a metallic shim stock layer. The flexible mesh may beincluded as a layer within a composite structure. The flexible mesh maybe located onto an aluminum surface, a steel surface, a polyethyleneterephthalate, or a thermoplastic epoxy surface. The flexible mesh maybe heat bonded or otherwise adhered to a woven or non-woven fibrousmaterial. The flexible mesh may be located onto a panel structure forforming a patch to stiffen the panel structure. The openings formed inthe mesh may assist in reducing read-through on the panel surface thatopposes the patch. The flexible mesh may be located onto a fiberglasslayer. The mesh may be located onto a vehicle door beam.

A fastener may be located into an opening of the flexible mesh to holdthe mesh in place at a desired location. The fastener may have a headportion having a diameter that is larger than the diameter of theopening in the flexible mesh that receives the fastener.

The activatable material may include a magnetic filler allowing theflexible mesh to be magnetically adhered to a metallic surface prior toactivation. The activatable material may be a sound and/or vibrationdamping material.

The flexible mesh may be located onto a first surface of an adhesive orsealant material as a handling layer and the second surface of theadhesive or sealant material is covered by a release liner. The releaseliner may be perforated and a plurality of metallic spheres are locatedonto the perforated portions of the adhesive or sealant material so thatthe metallic spheres adhere to the adhesive or sealant only at theperforated portions where the adhesive or sealant is exposed. Aplurality of metallic spheres may be located onto the adhesive orsealant material through the openings in the flexible mesh so that themetallic spheres adhere to the adhesive or sealant only at the openingsin the flexible mesh where the adhesive or sealant is exposed. Themetallic spheres may be located into a tray and the adhesive or sealantis brought into contact with the tray so that the metallic spheresadhere to the adhesive or sealant where it is exposed. The perforationsmay be formed in a desired pattern so that the metallic spheres arelocated in only specific locations as required for sealing a joint orfacilitating an induction heating process. The metallic spheres may beheated prior to deposition onto the article. Each opening in theflexible mesh may receive an average of at least 1 metallic sphere, atleast 3 metallic spheres, at least 4 metallic spheres, at least 6metallic spheres or even at least 8 metallic spheres.

The flexible mesh may be formed by extrusion, die-cutting, or lasercutting. The flexible mesh may be located onto a vehicle surface forbonding to an interior vehicle component. The interior vehicle componentmay include one or more curved surfaces and the flexible nature of theflexible mesh allows for conforming to the shape of the vehiclecomponent. The flexible mesh may be formed of a material that expandswhich provides a soft interface material between the vehicle surface andthe interior vehicle component.

The flexible mesh may be formed of at least two distinct materials asdescribed herein. A first material may be laid in a first direction anda second material may be laid in a second direction that is differentfrom the first direction. The first direction may be at an angle that isskew as related to the angle of the second direction.

The activatable material for forming the mesh may be an expandablematerial. The activatable material may expand upon exposure to astimulus and any openings in the mesh become closed as a result ofexpansion of the material. The openings formed in the mesh may allow fora consistent thickness of the activatable material post expansion andmay prevent unwanted surface irregularities from forming in the expandedmaterial.

The teachings herein include the formation of an adhesive, sealant orstructural material into a mesh sheet for use in bonding. The bondingmay occur with a vehicle interior structure or may involve bonding ofmetallic components that form the frame/panel/cavity portions of avehicle. Typically vehicle interior materials include the use ofpolypropylene as support structures and there are a number of challengesin bonding a secondary material (e.g., an interior material) topolypropylene. The teachings herein are directed to a polymer-basedadhesive. The polymer-based adhesive may include the addition of ametallic component (e.g., a ferromagnetic material as one example) sothat upon exposing the adhesive described herein to an induction heatingsource, the adhesive activates quickly and the induction heating sourcecauses the temperature of the interface between the adhesive and thepolypropylene to a temperature of at least about 300° F., at least about400° F., or even at least about 500° F., thereby causing improvedadhesion to the polypropylene.

An adhesive/sealant mesh in accordance with the present teachings may beapplied along the entirety of, or alternatively along only a portion ofthe surface to which adhesion is desired. Furthermore, the activatedadhesive/sealant mesh described herein, may impart a desired flexibilityto the surface due to the soft to the touch nature of the activatedadhesive. The adhesive/sealant mesh is both lighter than a typical fullsheet of adhesive/sealant and is also easier to apply to a surface ofthe interior panel. Furthermore, in the event that a surface to whichthe adhesive/sealant mesh is applied is a curved surface, the mesharrangement is much easier to apply in a curved fashion than a solidsheet of adhesive/sealant.

It is also possible that the adhesive/sealant mesh may activate toexpand (e.g., foam), such expansion acting to bridge a gap in betweentwo surfaces. Efforts to bond two fairly large surfaces often resultdistortion, warping, or buckling of one or more of the surfaces duringheating. The mesh arrangement (e.g., netting) acts to break up theinternal stress caused by adhesion and movement. Therefore deleteriouseffects on the surfaces are minimized upon exposure to heat.

The mesh format described herein may also be used for materials that areconsidered, structural support materials. One such material is astiffening patch which may be utilized to stiffen a portion of or anentirety of a panel utilized in a transportation vehicle. To addressfuel economy (CAFE standards) vehicles are being manufactured utilizingthinner gauged metal. Thinner metal is also more flexible which canrequire, depending on location and contour/styling, a strategicallyplaced panel stiffener on the inside of a panel to improve thestiffness. Panel stiffeners are typically engineered to be strong andrigid. These combined opposing properties can cause a visible distortionof the metal surface known as read-through. Thermosetting panelstiffeners typically yield high exotherms and shrink during thecrosslinking process and further distort the substrate surface. The useof a structural support material in a mesh format acts to minimize oreven eliminate the visible distortion caused by stress from thermalexpansion and also diffuses the heat caused by crosslinking. Continuousstiffening structures (e.g., those without openings as in the describedmesh material) tend to negatively focus the stress caused by thecoefficient of thermal expansion of the panel substrate and thestiffener patch which leads to a distinct visible profile of thestiffener patch that telegraphs through Class A surfaces such asautomotive surfaces. Breaking up the stress into smaller “zones” (e.g.,by use of the discontinuous mesh format) diffuses the concentration ofthe stress and thus diffuses the read-through.

The mesh may comprise more than one material. As one non-limitingexample, two different materials (e.g., different adhesives, sealants,or structural materials or some combination thereof), may be arranged inopposing directions so that rows of a first material are arrangedperpendicular to rows of a second material for forming the mesh.Alternatively, the different materials can be arranged in alternatinglayers to form a mesh composite. One mesh material could be elastomericor magnetic for attachment purposes while the other material is a panelstiffener adhesive. One mesh material could be tuned to counter theeffect of thermal expansion and cure shrinkage. A first mesh layer mayserve as an attachment layer. A second mesh layer may serve as astructural panel stiffener layer. A third mesh layer may be a fiberglassbonding layer. A first mesh layer may serve as an attachment layer. Asecond mesh layer may serve as a structural panel stiffener layer. Athird mesh layer may be a carrier layer. A first mesh layer may serve aspanel stiffening layer. A second mesh layer may serve as a tensilestrength increasing layer (e.g., fiberglass).

The mesh may be formed as a sleeve to surround a portion of a part. Themesh material may expand to cover a desired area of that part afteractivation. Specifically, the mesh sleeve may be fitted about a vehicledoor beam or roof bow. The mesh sleeve may be self-fastening. The meshsleeve may be formed of multiple layers.

The mesh may be used to provide acoustic properties. The mesh may beformed as an acoustic blanket to prevent or at least attenuate thetransmission of sound through a vehicle cavity.

The mesh may comprise a lightweight expandable acoustic foam. As oneexample, about 1.5 pounds of mesh may cover 25 square feet of area with4 mm of foam. The mesh size (e.g., the size of the openings locatedwithin the mesh) can be tuned for continuous coverage so that theexpanding foam grid grows into itself forming a continuous layer. A fullsheet of continuous coverage expandable material can lead to internalexpansion stress which causes undesirable buckling and unwanted voids.The mesh configuration isolates the stress into predictable patterns.The mesh configuration conforms to curved surfaces better than acontinuous configuration. The structure (e.g., size, shape, andconfiguration) of the mesh and the material itself can be tuned tocreate “acoustic” pockets.

The materials for forming the mesh described herein can be selected froma wide variety of materials but may be selected from adhesives, sealantsand structural support materials. The mesh material may include one ormore additional polymers or copolymers, which can include a variety ofdifferent polymers, such as thermoplastics, elastomers, plastomerscombinations thereof or the like. For example, and without limitation,polymers that might be appropriately incorporated into the polymericadmixture include halogenated polymers, polycarbonates, polyketones,urethanes, polyesters, silanes, sulfones, allyls, olefins, styrenes,acrylates, methacrylates, epoxies, silicones, phenolics, rubbers,polyphenylene oxides, terphthalates, acetates (e.g., EVA), acrylates,methacrylates (e.g., ethylene methyl acrylate polymer) or mixturesthereof. Other potential polymeric materials may be or may include,without limitation, polyolefin (e.g., polyethylene, polypropylene)polystyrene, polyacrylate, poly(ethylene oxide), poly(ethyleneimine),polyester, polyurethane, polysiloxane, polyether, polyphosphazine,polyamide, polyimide, polyisobutylene, polyacrylonitrile, poly(vinylchloride), poly(methyl methacrylate), poly(vinyl acetate),poly(vinylidene chloride), polytetrafluoroethylene, polyisoprene,polyacrylamide, polyacrylic acid, polymethacrylate.

When used, these polymers can comprises a small portion or a moresubstantial portion of the mesh material (e.g., up to 85% by weight orgreater). Preferably, the one or more additional polymers comprisesabout 0.1% to about 50%, more preferably about 1% to about 20% and evenmore preferably about 2% to about 10% by weight of the mesh material.

The mesh materials may include one or more polymeric materials includingone or more ethylene copolymers and/or terpolymers. The ethylenecopolymers and/or terpolymers may include but are not limited toethylene methyl acrylate (EMA) and/or ethylene vinyl acetate (EVA). Atleast about 20%, at least 40%, or even at least 60% of the mesh materialmay comprise an ethylene copolymer.

The mesh materials may also include epoxy-based materials, which maycontain an epoxy resin. Epoxy resin is used herein to mean any of theconventional dimeric, oligomeric or polymeric epoxy materials containingat least one epoxy functional group. Moreover, the term epoxy resin canbe used to denote one epoxy resin or a combination of multiple epoxyresins. The mesh materials may be epoxy-containing materials having oneor more oxirane rings polymerizable by a ring opening reaction. Inpreferred embodiments, the mesh material includes up to about 80% ormore of an epoxy resin. More preferably, the mesh material includesbetween about 2% and 70% by weight epoxy resin, more preferably betweenabout 4% and 30% by weight epoxy resin and even more preferably betweenabout 7% and 18% by weight epoxy resin. Of course, amounts of epoxyresin may be greater or lower depending upon the intended application ofthe mesh material. As an example, it is contemplated that weightpercentages may be lower or higher when other ingredients such as theadduct, filler, alternative polymers, combinations thereof or the likeare used in greater or lesser weight percentages.

The epoxy may be aliphatic, cycloaliphatic, aromatic or the like. Theepoxy may be supplied as a solid (e.g., as pellets, chunks, pieces orthe like) or a liquid (e.g., an epoxy resin). As used herein, unlessotherwise stated, a resin is a solid resin if it is solid at atemperature of 23° C. and is a liquid resin if it a liquid at 23° C. Theepoxy may include an ethylene copolymer or terpolymer that may possessan alpha-olefin. As a copolymer or terpolymer, the polymer is composedof two or three different monomers, i.e., small molecules with highchemical reactivity that are capable of linking up with similarmolecules. Preferably, an epoxy resin is added to the mesh material toincrease the adhesion, flow properties or both of the material. Oneexemplary epoxy resin may be a phenolic resin, which may be a novalactype or other type resin. Other preferred epoxy containing materials mayinclude a bisphenol-A epichlorohydrin ether polymer, or a bisphenol-Aepoxy resin which may be modified with butadiene or another polymericadditive. Moreover, various mixtures of several different epoxy resinsmay be employed as well. Examples of suitable epoxy resins are soldunder the tradename DER® (e.g., DER 331, DER 661, DER 662), commerciallyavailable from the Dow Chemical Company, Midland, Mich.

The mesh material may also include one or more adducts. While it iscontemplated that various polymer/elastomer adducts may be employedaccording to the present invention, one preferred adduct is anepoxy/elastomer adduct. An elastomer-containing adduct may be employedin the mesh material of the present invention in a relatively highconcentration. The epoxy/elastomer hybrid or adduct may be included inan amount of up to about 80% by weight of the adhesive material. Morepreferably, the elastomer-containing adduct is approximately at least5%, more typically at least 7% and even more typically at least 10% byweight of the mesh material can be up to 60% or more, but morepreferably is about 10% to 30% by weight of the mesh material. Ofcourse, the elastomer-containing adduct may be a combination of two ormore particular adducts and the adducts may be solid adducts or liquidadducts at a temperature of 23° C. or may also be combinations thereof.In one preferred embodiment, the adduct is composed of substantiallyentirely (i.e., at least 70%, 80%, 90% or more) of one or more adductsthat are solid at a temperature of 23° C.

The adduct itself generally includes about 1:5 to 5:1 parts of epoxy orother polymer to elastomer, and more preferably about 1:3 to 3:1 partsor epoxy to elastomer. More typically, the adduct includes at leastabout 5%, more typically at least about 12% and even more typically atleast about 18% elastomer and also typically includes not greater thanabout 50%, even more typically no greater than about 40% and still moretypically no greater than about 35% elastomer, although higher or lowerpercentages are possible. Exemplary elastomers include, withoutlimitation, natural rubber, styrene-butadiene rubber, polyisoprene,polyisobutylene, polybutadiene, isoprene-butadiene copolymer, neoprene,nitrile rubber (e.g., a butyl nitrile, such as carboxy-terminated butylnitrile), butyl rubber, polysulfide elastomer, acrylic elastomer,acrylonitrile elastomers, silicone rubber, polysiloxanes, polyesterrubber, diisocyanate-linked condensation elastomer, EPDM(ethylene-propylene diene rubbers), chlorosulphonated polyethylene,fluorinated hydrocarbons, hydrocarbon resins and the like. In oneembodiment, recycled tire rubber is employed. An example of a preferredepoxy/elastomer adducts is sold under the tradename HYPDX RK 8-4commercially available from CVC Chemical. Examples of additional oralternative epoxy/elastomer or other adducts suitable for use in thepresent invention are disclosed in U.S. Patent Publication 2004/0204551,which is incorporated herein by reference for all purposes.

The elastomer-containing adduct, when added to the mesh material,preferably is added to modify structural properties of the mesh materialsuch as strength, toughness, stiffness, flexural modulus, or the like.Additionally, the elastomer-containing adduct may be selected to renderthe mesh material more compatible with coatings such as water-bornepaint or primer system or other conventional coatings.

In certain embodiments, it may be desirable to include one or morethermoplastic polyethers and/or thermoplastic epoxy resins in the meshmaterial. When included, the one or more thermoplastic polyetherspreferably comprise between about 1% and about 90% by weight of the meshmaterial, more preferably between about 3% and about 60% by weight ofthe mesh material and even more preferably between about 4% and about25% by weight of the mesh material. As with the other materials,however, more or less thermoplastic polyether may be employed dependingupon the intended use of the mesh material.

The mesh material may have at least one epoxide group may be ahydroxy-phenoxyether polymer, such as a polyetheramine thermoplasticmaterial as described herein. For example, such thermoplastic polymericmaterial having at least one epoxide group may be a product (e.g., athermoplastic condensation reaction product) of a reaction of amono-functional or di-functional species (i.e., respectively, a specieshaving one or two reactive groups, such as an amide containing species),with an epoxide-containing moiety, such as a diepoxide (i.e., a compoundhaving two epoxide functionalities), reacted under conditions forcausing the hydroxyl moieties to react with the epoxy moieties to form agenerally linear backbone polymer chain with ether linkages.

The thermoplastic polyethers typically include pendant hydroxylmoieties. The thermoplastic polyethers may also include aromaticether/amine repeating units in their backbones. The thermoplasticpolyethers of the present invention preferably have a melt index betweenabout 5 and about 100, more preferably between about 25 and about 75 andeven more preferably between about 40 and about 60 grams per 10 minutesfor samples weighing 2.16 Kg at a temperature of about 190° C. Ofcourse, the thermoplastic polyethers may have higher or lower meltindices depending upon their intended application. Preferredthermoplastic polyethers include, without limitation, polyetheramines,poly(amino ethers), copolymers of monoethanolamine and diglycidyl ether,combinations thereof or the like.

Preferably, the thermoplastic polyethers are formed by reacting an aminewith an average functionality of 2 or less (e.g., a difunctional amine)with a glycidyl ether (e.g., a diglycidyl ether). As used herein, theterm difunctional amine refers to an amine with an average of tworeactive groups (e.g., reactive hydrogens).

According to one embodiment, the thermoplastic polyether is formed byreacting a primary amine, a bis(secondary) diamine, a cyclic diamine, acombination thereof or the like (e.g., monoethanolamine) with adiglycidyl ether or by reacting an amine with an epoxy-functionalizedpoly(alkylene oxide) to form a poly(amino ether). According to anotherembodiment, the thermoplastic polyether is prepared by reacting adifunctional amine with a diglycidyl ether or diepoxy-functionalizedpoly(alkylene oxide) under conditions sufficient to cause the aminemoieties to react with the epoxy moieties to form a polymer backbonehaving amine linkages, ether linkages and pendant hydroxyl moieties.Optionally, the polymer may be treated with a monofunctional nucleophilewhich may or may not be a primary or secondary amine.

Additionally, it is contemplated that amines (e.g., cyclic amines) withone reactive group (e.g., one reactive hydrogen) may be employed forforming the thermoplastic polyether. Advantageously, such amines mayassist in controlling the molecular weight of the thermoplastic etherformed.

Examples of preferred thermoplastic polyethers and their methods offormation are disclosed in U.S. Pat. Nos. 5,275,853; 5,464,924 and5,962,093, which are incorporated herein by reference for all purposes.Advantageously, the thermoplastic polyethers can provide the meshmaterial with various desirable characteristics such as desirablephysical and chemical properties for a wide variety of applications asis further described herein.

It is possible that the mesh material includes at least one impactmodifier. As used herein, like with any other ingredients of the presentinvention, the term “impact modifier” can include one impact modifier orplural impact modifiers. Various impact modifiers may be employed in thepractice of the present invention and often include one or moreelastomers. It is generally preferable for the impact modifier to be atleast 4%, more typically at least 7%, even more typically at least 10%,still more typically at least 13% and even still more typically at least16% by weight of the mesh material and also preferable for the impactmodifier to be less than 90%, more typically less than 40% an even moretypically less than 30% by weight of the mesh material, although higheror lower amounts may be used in particular embodiments.

In one embodiment of the present invention, the impact modifier includesat least one shell/core impact modifier and preferably the impactmodifier includes a substantial portion of core/shell impact modifier.In one preferred embodiment, the impact modifier is comprised of atleast 60%, more typically at least 80% and even more typically at least97% core/shell impact modifier. As used herein, the term core/shellimpact modifier denotes an impact modifier wherein a substantial portion(e.g., greater than 30%, 50%, 70% or more by weight) thereof iscomprised of a first polymeric material (i.e., the first or corematerial) that is substantially entirely encapsulated by a secondpolymeric material (i.e., the second or shell material). The first andsecond polymeric materials, as used herein, can be comprised of one,two, three or more polymers that are combined and/or reacted together(e.g., sequentially polymerized) or may be part of separate or samecore/shell systems.

The first and second polymeric materials of the core/shell impactmodifier can include elastomers, polymers, thermoplastics, copolymers,other components, combinations thereof or the like. In preferredembodiments, the first polymeric material, the second polymeric materialor both of the core/shell impact modifier include or are substantiallyentirely composed of (e.g., at least 70%, 80%, 90% or more by weight)one or more thermoplastics. Exemplary thermoplastics include, withoutlimitation, styrenics, acrylonitriles, acrylates, acetates, polyamides,polyethylenes or the like.

Preferred core/shell impact modifiers are formed by emulsionpolymerization followed by coagulation or spray drying. It is alsopreferred for the impact modifier to be formed of or at least include acore-shell graft co-polymer. The first or core polymeric material of thegraft copolymer preferably has a glass transition temperaturesubstantially below (i.e., at least 10, 20, 40 or more degreescentigrade) the glass transition temperature of the second or shellpolymeric material. Moreover, it may be desirable for the glasstransition temperature of the first or core polymeric material to bebelow 23° C. while the glass temperature of the second or shellpolymeric material to be above 23° C., although not required.

Examples of useful core-shell graft copolymers are those where hardcontaining compounds, such as styrene, acrylonitrile or methylmethacrylate, are grafted onto core made from polymers of soft orelastomeric containing compounds such as butadiene or butyl acrylate.U.S. Pat. No. 3,985,703, which is herein incorporated by reference,describes useful core-shell polymers, the cores of which are made frombutyl acrylate but can be based on ethyl isobutyl, 2-ethylhexel or otheralkyl acrylates or mixtures thereof. The core polymer, may also includeother copolymerizable containing compounds, such as styrene, vinylacetate, methyl methacrylate, butadiene, isoprene, or the like. The corepolymer material may also include a cross linking monomer having two ormore nonconjugated double bonds of approximately equal reactivity suchas ethylene glycol diacrylate, butylene glycol dimethacrylate, and thelike. The core polymer material may also include a graft linking monomerhaving two or more nonconjugated double bonds of unequal reactivity suchas, for example, diallyl maleate and allyl methacrylate.

One or more blowing agents may be added to the mesh material forproducing inert gasses that form, as desired, an open and/or closedcellular structure within the mesh material. In this manner, it may bepossible to lower the density of articles fabricated from the material.In addition, the material expansion can help to improve sealingcapability, acoustic damping or both.

The blowing agent may include one or more nitrogen containing groupssuch as amides, amines and the like. Examples of suitable blowing agentsinclude azodicarbonamide, dinitrosopentamethylenetetramine,azodicarbonamide, dinitrosopentamethylenetetramine,4,4_(i)-oxy-bis-(benzenesulphonylhydrazide), trihydrazinotriazine andN,N_(i)-dimethyl-N,N_(i)-dinitrosoterephthalamide.

An accelerator for the blowing agents may also be provided in the meshmaterial. Various accelerators may be used to increase the rate at whichthe blowing agents form inert gasses. One preferred blowing agentaccelerator is a metal salt, or is an oxide, e.g. a metal oxide, such aszinc oxide. Other preferred accelerators include modified and unmodifiedthiazoles or imidazoles.

Amounts of blowing agents and blowing agent accelerators can vary widelywithin the mesh material depending upon the type of cellular structuredesired, the desired amount of expansion of the mesh material, thedesired rate of expansion and the like. Exemplary ranges for the amountsof blowing agents and blowing agent accelerators in the mesh materialrange from about 0.001% by weight to about 5% by weight and arepreferably in the mesh material in fractions of weight percentages.

In one embodiment, the present invention contemplates the omission of ablowing agent. Preferably, however, the material, the blowing agent orboth of the present invention are thermally activated. Alternatively,other agents may be employed for realizing activation by other means,such as moisture, radiation, or otherwise.

One or more curing agents and/or curing agent accelerators may be addedto the mesh material. Amounts of curing agents and curing agentaccelerators can, like the blowing agents, vary widely within the meshmaterial depending upon the type of cellular structure desired, thedesired amount of expansion of the mesh material, the desired rate ofexpansion, the desired structural properties of the mesh material andthe like. Exemplary ranges for the curing agents or curing agentaccelerators present in the mesh material range from about 0.001% byweight to about 7% by weight.

Preferably, the curing agents assist the mesh material in curing bycrosslinking of the polymers, epoxy resins or both. It is alsopreferable for the curing agents to assist in thermosetting the meshmaterial. Useful classes of curing agents are materials selected fromaliphatic or aromatic amines or their respective adducts, amidoamines,polyamides, cycloaliphatic amines, anhydrides, polycarboxylicpolyesters, isocyanates, phenol-based resins (e.g., phenol or cresolnovolak resins, copolymers such as those of phenol terpene, polyvinylphenol, or bisphenol-A formaldehyde copolymers, bishydroxyphenyl alkanesor the like), or mixtures thereof. Particular preferred curing agentsinclude modified and unmodified polyamines or polyamides such astriethylenetetramine, diethylenetriamine tetraethylenepentamine,cyanoguanidine, dicyandiamides and the like. An accelerator for thecuring agents (e.g., a modified or unmodified urea such as methylenediphenyl bis urea, an imidazole or a combination thereof) may also beprovided for preparing the mesh material. The mesh material may alsoinclude one or more fillers, including but not limited to particulatedmaterials (e.g., powder), beads, microspheres, or the like. Preferablythe filler includes a material that is generally non-reactive with theother components present in the mesh material. While the fillers maygenerally be present within the mesh material to take up space at arelatively low weight, it is contemplated that the fillers may alsoimpart properties such as strength and impact resistance to the meshmaterial.

Examples of fillers include calcium carbonate, silica, diatomaceousearth, glass, clay (e.g., including nanoclay), talc, pigments,colorants, glass beads or bubbles, glass, carbon or ceramic fibers,nylon or polyamide fibers (e.g., Kevlar), antioxidants, and the like.Such fillers, particularly clays, can assist the mesh material inleveling itself during flow of the material. The clays that may be usedas fillers may include clays from the kaolinite, illite, chloritem,smecitite or sepiolite groups, which may be calcined. Examples ofsuitable fillers include, without limitation, talc, vermiculite,pyrophyllite, sauconite, saponite, nontronite, montmorillonite ormixtures thereof. The clays may also include minor amounts of otheringredients such as carbonates, feldspars, micas and quartz. The fillersmay also include ammonium chlorides such as dimethyl ammonium chlorideand dimethyl benzyl ammonium chloride. Titanium dioxide might also beemployed.

A non-limiting example sealant/adhesive formulation for the mesh isprovided below:

TABLE A Chemical Name Percent of Formula Ethylene Methyl AcrylateCopolymer 25.00 Ethylene Vinyl Acetate Copolymer 20.00 OxidizedSynthetic Paraffin 20.71 DGEBPA-based polymer 3.00 Dicumyl Peroxide(40%) & Kaolin (60%) 1.00 Cyanoguanidine 0.20 Aromatic Hydrocarbon Resin7.74 Ground High Calcium Carbonate 22.25 Carbon Black 0.10 Total 100.00

The mesh as described herein may be utilized as a handling layer for anadhesive/sealant material which may be tacky and may also be activatable(e.g., expandable). Non-limiting examples of such adhesives are setforth in Table B:

TABLE B Chemical Name Formula A Formula B Brominated Olefin Polymer 5.76Ethylene Propylene Copolymer 9.00 Ethylene Propylene Terpolymer 1.926.00 Polybutadiene Adduct & Amorphous 1.20 Silica Aramide 0.07Ethylene-propylene rubber 4.80 Ethylene Acrylate Copolymer 4.80 EthyleneAcrylic copolymer 1.92 Carbon Black 0.29 9.00 Polybutene 26.00 10.54Hydrocarbon Resin 15.10 1.70 Calcium Carbonate Filler 34.79 23.70 SilicaFiller 0.06 Hydrocarbon Oil 14.16 Polyethylene Homopolymer 2.00Azodicarbonamide 0.09 Phenolic Resin 1.00 Iron Phosphide 20.70 ZincOxide 2.00 1.50 Sulfur 0.30 Dipentaerythritol Pentaacrylate 0.201,1-bis(t-butylperoxy)-3,3,5-trimethyl 1.20 cyclohexane & carbonic acidcalcium salt & silicic acid calcium salt Dibenzoyl Peroxide &Dicyclohexyl 0.05 Phthalate 100.00 100.00

When employed, the fillers in the mesh material can range from 10% orless to 90% or greater by weight of the mesh material, but more typicalfrom about 30 to 55% by weight of the mesh material. According to someembodiments, the mesh material may include from about 0% to about 3% byweight, and more preferably slightly less than 1% by weight clays orsimilar fillers. Powdered (e.g. about 0.01 to about 50, and morepreferably about 1 to 25 micron mean particle diameter) mineral typefiller can comprise between about 5% and 70% by weight, more preferablyabout 10% to about 50% by weight.

The mesh may be employed in the form of a random arrangement, or in agenerally ordered relationship (e.g., according to a predeterminedpattern) relative to each other. The openings formed in the mesh may beevenly spaced from one another throughout the mesh. Alternatively, thespaces in between the openings may change from opening to opening tofacilitate more constricted areas in the mesh (possibility facilitatingcurvature of the mesh) and also looser portions of the mesh (possible topermit flat lying portions of the mesh). In one non-limiting example,the mesh may be formed into a sleeve, whereby the sleeve is moreconstricted about a center portion of the sleeve (e.g., the diameter issmaller around the center while the diameter is larger at the ends ofthe sleeve).

As shown for example in FIGS. 1 and 2, the mesh 10 may include multiplelayers including a first layer 12, a second layer 14, and a third layer16. It is possible that each layer 12, 14, 16 comprises a differentmaterial or one or more of the layers 12, 14, 16 may comprise the samematerial as another layer. The mesh 10 further includes a plurality ofopenings 18 formed in the material. Additionally, as shown in FIG. 2,the mesh 10 may be disposed on a solid material layer 20. A plurality ofparticles, such as spheres, metallic spheres, or the like may bepositioned in the openings 18 of the mesh 10 on the solid material layer20.

As used herein, unless otherwise stated, the teachings envision that anymember of a genus (list) may be excluded from the genus; and/or anymember of a Markush grouping may be excluded from the grouping.

Unless otherwise stated, any numerical values recited herein include allvalues from the lower value to the upper value in increments of one unitprovided that there is a separation of at least 2 units between anylower value and any higher value. As an example, if it is stated thatthe amount of a component, a property, or a value of a process variablesuch as, for example, temperature, pressure, time and the like is, forexample, from 1 to 90, preferably from 20 to 80, more preferably from 30to 70, it is intended that intermediate range values such as (forexample, 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc.) are within theteachings of this specification. Likewise, individual intermediatevalues are also within the present teachings. For values which are lessthan one, one unit is considered to be 0.0001, 0.001, 0.01, or 0.1 asappropriate. These are only examples of what is specifically intendedand all possible combinations of numerical values between the lowestvalue and the highest value enumerated are to be considered to beexpressly stated in this application in a similar manner. As can beseen, the teaching of amounts expressed as “parts by weight” herein alsocontemplates the same ranges expressed in terms of percent by weight.Thus, an expression in the of a range in terms of “at least ‘x’ parts byweight of the resulting composition” also contemplates a teaching ofranges of same recited amount of “x” in percent by weight of theresulting composition.”

Unless otherwise stated, all ranges include both endpoints and allnumbers between the endpoints. The use of “about” or “approximately” inconnection with a range applies to both ends of the range. Thus, “about20 to 30” is intended to cover “about 20 to about 30”, inclusive of atleast the specified endpoints.

The disclosures of all articles and references, including patentapplications and publications, are incorporated by reference for ailpurposes. The term “consisting essentially of to describe a combinationshall include the elements, ingredients, components or steps identified,and such other elements ingredients, components or steps that do notmaterially affect the basic and novel characteristics of thecombination. The use of the terms “comprising” or “including” todescribe combinations of elements, ingredients, components or stepsherein also contemplates embodiments that consist of, or consistessentially of the elements, ingredients, components or steps.

Plural elements, ingredients, components or steps can be provided by asingle integrated element, ingredient, component or step. Alternatively,a single integrated element, ingredient, component or step might bedivided into separate plural elements, ingredients, components or steps.The disclosure of “a” or “one” to describe an element, ingredient,component or step is not intended to foreclose additional elements,ingredients, components or steps.

It is understood that the above description is intended to beillustrative and not restrictive. Many embodiments as well as manyapplications besides the examples provided will be apparent to those ofskill in the art upon reading the above description. The scope of theinvention should, therefore, be determined not with reference to theabove description, but should instead be determined with reference tothe appended claims, along with the full scope of equivalents to whichsuch claims are entitled. The disclosures of all articles andreferences, including patent applications and publications, areincorporated by reference for all purposes. The omission in thefollowing claims of any aspect of subject matter that is disclosedherein is not a disclaimer of such subject matter, nor should it beregarded that the inventors did not consider such subject matter to bepart of the disclosed inventive subject matter.

What is claimed is:
 1. An article, comprising: a first flexible meshlayer pliable enough for being arranged in direct planar contact with acontoured surface, the mesh layer comprising an activatable material andproviding one or more attributes of adhering, sealing, reinforcing oracting as a handling film to a surface receiving the mesh layer; asecond flexible mesh layer disposed over the first flexible mesh layerand extending in a direction perpendicular to the first flexible meshlayer, thereby forming openings between the first flexible mesh layerand the second flexible mesh layer; a solid material layer whichreceives the first flexible mesh layer; and a plurality of rigid spheresdispersed on a surface of the solid material layer and positioned withinthe openings between the first flexible mesh layer and the secondflexible mesh layer prior to activation of the activatable material;wherein the first flexible mesh layer is an attachment layer to securethe article to the contoured surface and the second flexible mesh layeris a stiffening layer.
 2. The article of claim 1, wherein the solidmaterial layer is an adhesive or sealant material.
 3. The article ofclaim 1, wherein the solid material layer has a thickness (t) and theplurality of rigid spheres have a max diameter (d) wherein the thicknesst is greater than the max diameter d.
 4. The article of claim 1, whereinthe plurality of rigid spheres are metallic.
 5. The article of claim 4,wherein the plurality of rigid spheres comprise aluminum oxide spheres.6. The article of claim 1, further comprising a metallic filler includedin the activatable material.
 7. The article of claim 6, wherein themetallic filler allows for induction heating of the activatablematerial.
 8. The article of claim 1, wherein the article is located incontact with an end of a drain tube to seal an interface between a draintube and vehicle structure to which the drain tube is attached.
 9. Thearticle of claim 1, wherein the article is formed as a sleeve having adiameter smaller about a central portion than a diameter near an end ofthe sleeve.
 10. The article of claim 1, wherein the activatable materialis an expandable material.
 11. The article of claim 1, wherein the firstflexible mesh layer is sufficiently flexible that it collapses under itsown weight when held at one end.
 12. The article of claim 2, wherein thefirst flexible mesh layer and the second flexible mesh layer are formedhaving a plurality of repeating generally diamond shaped, rectangular,circular or square openings.
 13. The article of claim 1, wherein afastener is located into one of the openings between the first flexiblemesh layer and the second flexible mesh layer to hold the article inplace at a desired location.
 14. The article of claim 13, wherein thefastener has a head portion having a diameter that is larger than thediameter of the opening that receives the fastener.
 15. The article ofclaim 1, wherein the activatable material expands upon exposure to astimulus and any openings in the article become closed as a result ofexpansion of the material.
 16. The article of claim 15, wherein theopenings formed in the article allow for a consistent thickness of theactivatable material post expansion and prevents unwanted surfaceirregularities from forming in the expanded material.
 17. The article ofclaim 1, wherein the activatable material includes a magnetic fillerallowing the first flexible mesh layer to be magnetically adhered to ametallic surface prior to activation.
 18. The article of claim 1,wherein the first flexible mesh layer is included as a layer within acomposite structure.
 19. The article of claim 4, wherein the pluralityof rigid spheres are adhered to the solid material layer and at least 8metallic spheres are located in each of the openings.
 20. The article ofclaim 1, further comprising a third flexible mesh layer disposed overthe second flexible mesh layer and extending in a directionperpendicular to the second flexible mesh layer and parallel to thefirst flexible mesh layer, wherein the third flexible mesh layer is afiberglass bonding layer.